Huang Zheng-Hong, Xie Nan-Hong, Zhang Min, Xu Bo-Qing
Innovative Catalysis Program, Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
ChemSusChem. 2019 Jan 10;12(1):200-207. doi: 10.1002/cssc.201801886. Epub 2018 Nov 14.
Pyrolyzed base-metal-based metal-organic frameworks (MOFs) with FeN coordination are emerging as nonprecious metal catalysts for electrochemical oxygen reduction reaction (ORR). However, surprisingly, nonpyrolyzed MOFs involving Fe-N coordination have not been explored for the ORR. This study concerns the catalytic performance of a semiconducting nonpyrolyzed iron triazolate framework (FeTa ) for ORR in alkaline electrolyte. The FeTa catalyst is studied as composites with different amounts of conductive Ketjenblack carbon (KB). The performance of these FeTa -x KB (x denotes the KB/FeTa weight ratio) composites by onset and half-wave potentials of ORR appears to be superior to most previously documented nonpyrolyzed MOFs. Characterization by elemental analysis, FTIR spectroscopy, XPS, and cyclic voltammetry suggest that N-Fe -OH sites at the surface of FeTa function as the catalytic active sites. This FeTa also shows very stable activity during ORR, as supported by accelerated durability test of the FeTa -x KB sample (20 000 cycles, ca. 90 h). The framework structure of FeTa remains intact during the durability test, which would help to explain its excellent catalytic durability. This would be the first study demonstrating efficient and stable ORR catalysis by a nonpyrolyzed Fe-N coordination-based MOF material.
具有FeN配位的热解贱金属基金属有机框架(MOF)正在成为用于电化学氧还原反应(ORR)的非贵金属催化剂。然而,令人惊讶的是,尚未探索涉及Fe-N配位的非热解MOF用于ORR。本研究关注半导体非热解三唑铁框架(FeTa)在碱性电解质中对ORR的催化性能。研究了FeTa催化剂与不同量的导电科琴黑碳(KB)的复合材料。通过ORR的起始电位和半波电位对这些FeTa -x KB(x表示KB/FeTa重量比)复合材料的性能似乎优于大多数先前记录的非热解MOF。通过元素分析、FTIR光谱、XPS和循环伏安法表征表明,FeTa表面的N-Fe -OH位点作为催化活性位点。如FeTa -x KB样品的加速耐久性测试(20 000次循环,约90小时)所支持的,这种FeTa在ORR期间也显示出非常稳定的活性。FeTa的框架结构在耐久性测试期间保持完整,这将有助于解释其优异的催化耐久性。这将是第一项证明基于非热解Fe-N配位的MOF材料进行高效稳定ORR催化的研究。